Azo dyes containing a diazotized 5-amino isothiazol moiety having thereon a sulfonic acid or salt group

ABSTRACT

This invention relates to azo dyes in which the diazotized amino component bears a sulfonic acid or salt group on its ring. These dyes have excellent dyeing properties on polyamide fibers, particularly nylon carpets and also impart color to cellulose acetate fibers and wool. 
     The dyes correspond to the general formula: ##STR1## wherein R 1  is selected from hydrogen and alkyl; M is H + , Na + , K + , Li +  or NH 4   +  ; and the coupler C is selected from a variety of couplers including anilines, tetrahydroquinolines, phenols , and the like which may be substituted with known substituents such as halogen, alkyl, alkoxy, acylamido, sulfamoyl, carbamoyl and the like.

This invention concerns novel dyes in which the diazo moiety contains asulfonic acid or salt group. These dyes are substantially water solubleand are particularly useful for dyeing polyamide, wool and the like, andexhibit excellent properties, including fastness to light anddyeability.

The dyes of this invention correspond to he general formula: ##STR2##wherein R¹ is hydrogen or alkyl; M is H⁺, Na⁺, Li⁺, K⁺ or NH₄ ⁺ ; and Cis any of a variety of couplers as defined below.

More particularly, the dyes are of the above formula wherein the couplerC is selected from those having the formulas ##STR3## wherein R² and R¹⁴each represents up to three groups selected from hydrogen, fluorine,chlorine, bromine, alkyl, cycloalkyl, alkoxy, phenoxy, alkylthio,arylthio, and radicals having the formula --NH--X--R³ in which X is--CO--, --COO--, or --SO₂ -- and R³ is selected from alkyl and alkylsubstituted with halogen, hydroxy, phenoxy, aryl, cyano, cycloalkyl,alkylsulfonyl, alkylthio, alkanoyloxy, and alkoxy, and when X is --CO--,R³ also is selected from hydrogen, amino, alkylamino, alkylcarbamoyl,dialkylamino, arylamino, aryl, and furyl;

R⁴ and R⁵ are each selected from hydrogen, alkyl, aryl, cycloalkyl, andR⁴ and R⁵ together can be the single, combined group --CH₂ CH₂ CH₂ CH₂CH₂ --, --CH₂ CH₂ OCH₂ CH₂ --, --CH₂ CH₂ --S--CH₂ CH₂ --, or --CH₂ CH₂--SO₂ --CH₂ CH₂ --;

R⁸ is one or two groups each selected from hydrogen, alkyl and alkylsubstituted with --CN, alkoxy, alkoxycarbonyl, alkoxycarbonyloxy,phenyl, cyclohexoxy, --OH, --Cl and Br;

R⁹, R¹⁰ and R¹¹ are each selected from hydrogen, alkyl, phenyl, orphenyl substituted with 1-3 groups selected from Cl, Br, alkyl oralkoxy, alkylthio, benzylthio, cyclohexylthio, phenylthio andsubstituted phenylthio;

Q and Q' are each selected from --CO--, --SO₂, or --CN; R¹² and R¹³ areeach selected from hydrogen; alkyl, hydroxyalkyl, alkoxy,alkoxycarbonylamino, trifluoromethyl, phenyl or phenyl substituted with1-3 groups selected from Cl, Br, alkyl or alkoxy, alkoxycarbonylalkyl,cyanoalkyl, amino, haloalkyl, alkylamino, alkylthio, benzylthio,cyclohexylthio, phenylthio and substituted phenylthio; R¹² and R¹³ maycombine to form an alkylene bridge of 2 or 3 carbons, or to form anarylene or cycloalkylene radical of 5-6 carbons connecting Q and Q'; R¹⁶and R¹⁷ are selected from hydrogen, cycloalkyl, aryl, alkyl, and alkylsubstituted with alkoxy, hydroxy, alkoxyalkoxy, hydroxyalkoxy,carbamoyl, sulfamoyl, acylamido, or alkylsulfonyl, and aryl substitutedwith hydroxyalkyl; e is 1 or 2; and t and t' are each 1 or zero. It isnoted that when t or t' is zero, the corresponding Q or Q' group is--CN;

Each of the aliphatic portions of the above alkyl, cycloaliphatic,alkoxy, alkanoyl and the like groups, as well as the aryl and aryloxygroups, may be substituted further with up to three of the following:hydroxy; halogen; cyano; succinimido; glutarimido; phthalimido;2-pyrrolidono; cyclohexyl; phenyl or phenyl substituted with alkyl,alkoxy, halogen, alkanoylamino, cyano or alkoxycarbonyl; alkanoylamino;sulfamoyl; alkylsulfamoyl; vinylsulfonyl; acrylamido; phthalimidinyl;benzoylsulfonicimidyl; alkylsulfonamido; phenylsulfonamido;alkoxycarbonylamino; alkylcarbamoyloxy; alkoxycarbonyl;alkoxycarbonyloxy; ##STR4## wherein Y is --NH--, --NH--alkyl--, --O--,--S--, or --CH₂ O--; --S--R⁶ wherein R⁶ is alkyl, phenyl, phenylsubstituted with halogen, alkyl, alkoxy, alkanoylamino, cyano, oralkoxycarbonyl, pyridyl, pyrimidinyl, benzoxazolyl, benzimidazolyl,benzothiazolyl, or ##STR5## --OXR³ ; --NH--X--R³ ; --X--R³ ; --CONR⁷ R⁷; --SO₂ NR⁷ R⁷ ;

wherein R³ and X are as defined above and each R⁷ is selected from H andR³ ; alkoxy; alkoxy substituted with hydroxy, cyano, alkanoyloxy, oralkoxy; phenoxy or phenoxy substituted with one or more of alkyl, alkoxyor halogen. All of the aliphatic portions of the various groups hereincontain from 1-6 carbons, and are straight or branched chain.

The dyes of this invention impart yellow to violet shades on fibers,particularly polyamides, and are especially useful for dyeing polyamide(nylon) carpets, giving good fastness to light, ozone, oxides ofnitrogen, washing, sublimation, crocking and the like, and having goodleveling, transfer, exhaustion, and build properties. The dyes alsoresist shade change on carpets treated with insecticides such asMalathion.

The 5-amino-3-methylisothiazole-4-sulfonic acid is prepared according tothe equation ##STR6## as disclosed in detail by D. L. Pain and E. W.Parnell, J. Chem. Soc. 1965, 7283.

The couplers used in this invention are prepared according to knownprocedures. The dyes may be prepared as follows:

Diazotization and Coupling of 5-Amino-3-methylisothiazole-4-sulfonicAcid

5-Amino-3-methylisothiazole-4-sulfonic acid (9.7 g., 0.05 m) was addedto 150 ml of 60% aqueous acetic acid. Concentrated sulfuric acid (3.0ml) was added and the mixture stirred at room temperature for 30 min.and then cooled to 0° C. A solution of nitrosyl sulfuric acid, preparedby adding 3.6 g. NaNO₂ to 25 ml of conc. H₂ SO₄, was added at 0°-5° C.The diazotization reaction mixture was stirred at 0°-5° C. for 2 hrs.and coupled with the following couplers:

EXAMPLE 1 3-Acetamido-N,N-diethylaniline EXAMPLE 25-Acetamido-N-cyclohexyl-2-methylaniline EXAMPLE 3N-Ethyl-N-2-phthalimidoethyl-m-toluidine EXAMPLE 4 2-PhenylindoleEXAMPLE 5N-Ethyl-7-propionamido-1,2,3,4-tetrahydro-2,2,4,7-tetramethylquinolineEXAMPLE 6 6-Phenylimidazo [2,1-b]-thiazole EXAMPLE 7N-3-Acetamidopropyl-1-naphthylamine EXAMPLE 82,3-Dihydro-3,6-dimethyl-N-ethyl-1,4-benzoxazine EXAMPLE 9N,N-Dibenzyl-m-toluidine EXAMPLE 10 N-(2-Carbamylethyl)-2-phenylindole

The above couplers (0.005 m each) were dissolved in 15-25 ml of 1:5 acid(1 part propionic:5 parts acetic acid) and the solutions chilled in anice-bath. A 0.005 m aliquot of the previously prepared diazoniniumsolution was added to each coupler. Sodium acetate was added to a pH ofabout 3.5. After allowing to stand for about 2 hrs., the couplingmixtures were diluted with saturated NaCl solution to a total volume ofabout 400 ml. The dyes were collected by filtration, washed withsaturated NaCl solution and dried in air. The dyes were dyed on nyloncarpet and produced orange to violet shades having good lightfastness.

This invention will be further illustrated by the following examplesalthough it will be understood that these examples are included merelyfor purposes of illustration and are not intended to limit the scope ofthe invention. The compounds listed in the tables below can be preparedby procedures well known to the art.

                                      TABLE 1                                     __________________________________________________________________________     ##STR7##                                                                     R.sup.1                                                                            R.sup.2    R.sup.4 R.sup.5    M                                          __________________________________________________________________________    H    H          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 NHCOCH.sub.3                                                             Na                                         H    H          C.sub.2 H.sub.5                                                                       C.sub.3 H.sub.7n                                                                         "                                          H    H          "       C.sub.2 H.sub.5                                                                          Na                                         CH.sub.3                                                                           H          CH.sub.3                                                                              C.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2                                                      H                                          CH.sub.3                                                                           H          C.sub.2 H.sub.4 OH                                                                    C.sub.2 H.sub.4 CN                                                                       K                                          CH.sub.3                                                                           3-CH.sub.3 C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 CN                                                                       Na                                         C.sub.4 H.sub.9n                                                                   3-CH.sub.3 C.sub.2 H.sub.4 OH                                                                    C.sub.2 H.sub.4 OH                                                                       Na                                         C.sub.4 H.sub.9n                                                                   2-CH.sub.33-Cl                                                                           H       CH.sub.2 C.sub.6 H.sub. 5                                                                K                                          C.sub.4 H.sub.9n                                                                   3-Cl       C.sub.6 H.sub.11                                                                      C.sub.2 H.sub.5                                                                          K                                          C.sub.4 H.sub.9n                                                                   3-NHCOCH.sub.3                                                                           C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 CN                                                                       Na                                         C.sub.4 H.sub.9n                                                                   "          "       C.sub.2 H.sub.4 CONH.sub.2                                                               K                                          C.sub.4 H.sub.9n                                                                   2-CH.sub.3 H       C.sub.2 H.sub.4 SO.sub.2 NH.sub.2                                                        Na                                         C.sub.4 H.sub.9n                                                                   2-OC.sub.6 H.sub.5                                                                       C.sub.2 H.sub.4 CN                                                                    C.sub.2 H.sub.4 N(COCH.sub.3).sub.2                                                      H                                          C.sub.4 H.sub.9n                                                                   3-SCH.sub.3                                                                              C.sub.2 H.sub.4 OCOCH.sub.3                                                           C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2 H.sub.5                                               K                                          C.sub.4 H.sub.9n                                                                   3-CH.sub.3 C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 OCOCH.sub.3                                                              Na                                         C.sub.2 H.sub.5                                                                    3-SC.sub.6 H.sub.5 C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2 H.sub.5                                               K                                          C.sub.2 H.sub.5                                                                    3-NHCOOCH.sub.3                                                                          C.sub.2 H.sub.4 OH                                                                    C.sub.2 H.sub.4 OH                                                                       Na                                         C.sub.2 H.sub.5                                                                    3-NHSO.sub.2 CH.sub.3                                                                    C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 CN                                                                       Na                                         C.sub.2 H.sub.5                                                                    2-OCH.sub.3, 5-NHCOCH.sub.3                                                              C.sub.2 H.sub.4 OCOCH.sub.3                                                           C.sub.2 H.sub.4 OCOCH.sub.3                                                              NH.sub.4                                   C.sub.2 H.sub.5                                                                    3-NHCOCH.sub.2 Cl                                                                        C.sub.2 H.sub.4 OH                                                                    C.sub.6 H.sub.11                                                                         K                                          C.sub.2 H.sub.5                                                                    3-NHCOC.sub.2 H.sub.4 OH                                                                 H       C.sub.2 H.sub.4 OH                                                                       K                                          C.sub.2 H.sub.5                                                                    2-CH.sub.3, 3-Cl                                                                         H       CH.sub.2 C.sub.6 H.sub.5                                                                 K                                          C.sub.2 H.sub.5                                                                    2-NHCONHC.sub.2 H.sub.5                                                                  C.sub.2 H.sub.4 OH                                                                    C.sub.2 H.sub.4 CN                                                                       NH.sub.4                                   C.sub.2 H.sub.5                                                                    2-NHCON(C.sub.2 H.sub.5).sub.2                                                           C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                          K                                          C.sub.3 H.sub.7n                                                                   3-CH.sub.3 C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.4 NHCOCH.sub.3                                                             H                                          C.sub.3 H.sub.7n                                                                   3-NHCOCH.sub.3                                                                           "       C.sub.2 H.sub.4 CONH.sub.2                                                               H                                          C.sub.3 H.sub.7n                                                                   H          "       C.sub.2 H.sub.4 NHCOCH.sub.3                                                             Na                                         CH.sub.3                                                                           H          CH.sub.2 CH.sub.2OCH.sub.2 CH.sub.2                                                              Na                                         CH.sub.3                                                                           H          CH.sub.2 CH.sub.2SCH.sub.2 CH.sub.2                                                              Na                                         CH.sub.3                                                                           H          CH.sub.2 CH.sub.2SO.sub.2CH.sub.2 CH.sub.2                                                       Na                                         CH.sub.3                                                                           H          CH.sub.2 CH.sub.2NHCH.sub.2 CH.sub.2                                                             Na                                         CH.sub.3                                                                           H          CH.sub.2 CH.sub.2N(COCH.sub.3)CH.sub.2 CH.sub.2                                                  Na                                         __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR8##                                                                     R.sup.1                                                                            R.sup.2    R.sup.8 R.sup.4     M                                         __________________________________________________________________________    H    7-CH.sub.3 2-CH.sub.3                                                                            C.sub.2 H.sub.5                                                                           K                                         H    "          "       CH.sub.2 C.sub.6 H.sub.5                                                                  "                                         H    H          2,2,4-(CH.sub.3).sub.3                                                                C.sub.2 H.sub.5                                                                           Na                                        CH.sub.3                                                                           H          "       C.sub.2 H.sub.5                                                                           Na                                        CH.sub.3                                                                           H          "       CH.sub.2 C.sub.6 H.sub.4p-COOCH.sub.3                                                     Na                                        CH.sub.3                                                                           7-CH.sub.3 2-CH.sub.3                                                                            C.sub.2 H.sub.4 NHCOCH.sub.3                                                              H                                         C.sub.4 H.sub.9n                                                                   7-NHCOCH.sub.3                                                                           H       C.sub.2 H.sub.4 OH                                                                        K                                         C.sub.4 H.sub.9n                                                                   "          "       C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                          Na                                        C.sub.4 H.sub.9n                                                                   5-CH.sub.3 "       "           K                                         C.sub.4 H.sub.9n                                                                   8-CH.sub.3 "       C.sub.2 H.sub.4 OCH.sub.3                                                                 NH.sub.4                                  C.sub.4 H.sub.9n                                                                   7-CH.sub.3 2,2,4-(CH.sub.3).sub.3                                                                C.sub.2 H.sub.5                                                                           K                                         C.sub.4 H.sub.9n                                                                   "          "       C.sub.2 H.sub.4 Cl                                                                        K                                         C.sub.4 H.sub.9n                                                                   "          "       CH.sub.2 C.sub.6 H.sub.11                                                                 K                                         C.sub.4 H.sub.9n                                                                   7-SC.sub.6 H.sub.5                                                                       "       C.sub.2 H.sub.4 SO.sub.2 NH.sub.2                                                         K                                         C.sub.4 H.sub.9n                                                                   7-NHCOOCH.sub.3                                                                          CH.sub.3                                                                              C.sub.2 H.sub.4 OH                                                                        Na                                        C.sub.2 H.sub.5                                                                    7-NHSO.sub.2 CH.sub.3                                                                    2-C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.4 CN                                                                        Na                                        C.sub.2 H.sub.5                                                                    7-OCH.sub.3, 5-NHCOCH.sub.3                                                              3-OCOCH.sub.3                                                                         C.sub.2 H.sub.4 OCOCH.sub.3                                                               NH.sub.4                                  C.sub.2 H.sub.5                                                                    7-NHCOCH.sub.2 Cl                                                                        3-OH    C.sub.6 H.sub.11                                                                          K                                         C.sub.2 H.sub.5                                                                    7-NHCOC.sub.2 H.sub.4 OH                                                                 3-CONH.sub.2                                                                          C.sub.2 H.sub.4 OH                                                                        K                                         C.sub.2 H.sub.5                                                                    7-CH.sub.3, 3-Cl                                                                         3-Cl    CH.sub.2 C.sub.6 H.sub.5                                                                  K                                         C.sub.2 H.sub.5                                                                    7-NHCONHC.sub.2 H.sub.5                                                                  3-OC.sub.6 H.sub.5                                                                    C.sub.2 H.sub.4 CN                                                                        NH.sub.4                                  C.sub.2 H.sub.5                                                                    7-NHCON(C.sub.2 H.sub.5).sub.2                                                           "       C.sub.2 H.sub.5                                                                           K                                         C.sub.2 H.sub.5                                                                    7-CH.sub.3 3-SC.sub.2 H.sub.5                                                                    C.sub.2 H.sub.4 NHCOCH.sub.3                                                              H                                         C.sub.2 H.sub.5                                                                    7-NHCOCH.sub.3                                                                           3-CONHC.sub.2 H.sub.5                                                                 C.sub.2 H.sub.4 CONH.sub.2                                                                H                                         C.sub.3 H.sub.7n                                                                   H          3-OCH.sub.3                                                                           C.sub.2 H.sub.4 NHCOCH.sub.3                                                              Na                                        __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________     ##STR9##                                                                     R.sup.1                                                                            R.sup.2    R.sup.8 R.sup.4     M                                         __________________________________________________________________________    H    H          H       CH(CH.sub.3).sub.2                                                                        K                                         H    H          H       CH.sub.2 C.sub.6 H.sub.5                                                                  K                                         H    6-CH.sub.3 3-CH.sub.3                                                                            C.sub.2 H.sub.5                                                                           Na                                        CH.sub.3                                                                           "          "       C.sub.2 H.sub.4 OH                                                                        H                                         CH.sub.3                                                                           "          "       C.sub.2 H.sub.4 SO.sub.2 NH.sub.2                                                         Na                                        CH.sub.3                                                                           "          "       CH.sub.2 C.sub.6 H.sub.4p-COOCH.sub.3                                                     K                                         C.sub.4 H.sub.9n                                                                   "          "       C.sub.2 H.sub.4 OCH.sub.3                                                                 K                                         C.sub.4 H.sub.9n                                                                   6-NHCOCH.sub.3                                                                           H       C.sub.2 H.sub.5                                                                           K                                         C.sub.4 H.sub.9n                                                                   "          3-CH.sub.3                                                                            "           K                                         C.sub.4 H.sub.9n                                                                   "          3-CH(CH.sub.3).sub.2                                                                  C.sub.2 H.sub.4 OCH.sub.3                                                                 Na                                        C.sub.4 H.sub.9n                                                                   "          "       C.sub.2 H.sub.5                                                                           K                                         C.sub.4 H.sub.9n                                                                   "          "       C.sub.2 H.sub.4 OH                                                                        NH.sub.4                                  C.sub.4 H.sub.9n                                                                   "          "       CH.sub.2 CH.sub.2 CONH.sub.2                                                              H                                         C.sub.4 H.sub.9n                                                                   6-NHCOOCH.sub.3                                                                          2-CH.sub.2 OH                                                                         C.sub.2 H.sub.4 OH                                                                        Na                                        C.sub.4 H.sub.9n                                                                   6-NHSO.sub.2 CH.sub.3                                                                    "       C.sub.2 H.sub.4 CN                                                                        Na                                        C.sub.2 H.sub.5                                                                    5-OCH.sub.3, 8-NHCOCH.sub.3                                                              "       C.sub.2 H.sub.4 OCOCH.sub.3                                                               NH.sub.4                                  C.sub.2 H.sub.5                                                                    6-NHCOCH.sub.2 Cl                                                                        2-CH.sub.2 CH.sub.3                                                                   C.sub.6 H.sub.11                                                                          K                                         C.sub.2 H.sub.5                                                                    6-NHCOC.sub.2 H.sub.4 OH                                                                 H       C.sub.2 H.sub.4 OH                                                                        K                                         C.sub.2 H.sub.5                                                                    5-CH.sub.3, 8-Cl                                                                         2-CH.sub.2 Cl                                                                         CH.sub.2 C.sub.6 H.sub.5                                                                  K                                         C.sub.2 H.sub.5                                                                    6-NHCONHC.sub.2 H.sub.5                                                                  2-CH.sub.2 Cl                                                                         C.sub.2 H.sub.4 CN                                                                        NH.sub. 4                                 C.sub.2 H.sub.5                                                                    6-NHCON(C.sub.2 H.sub.5).sub.2                                                           2-CH.sub.2 OC.sub.6 H.sub.5                                                           C.sub.2 H.sub.5                                                                           K                                         C.sub.2 H.sub.5                                                                    6-CH.sub.3 "       C.sub.2 H.sub.4 NHCOCH.sub.3                                                              H                                         C.sub.2 H.sub.5                                                                    6-NHCOCH.sub.3                                                                           2-C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                    C.sub.2 H.sub.4 CONH.sub.2                                                                H                                         C.sub.2 H.sub.5                                                                    H          "       C.sub.2 H.sub.4 NHCOCH.sub.3                                                              Na                                        __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________     ##STR10##                                                                    R.sup.1                                                                            R.sup.9 R.sup.2    R.sup.4    M                                          __________________________________________________________________________    H    C.sub.6 H.sub.5                                                                       H          H          Na                                         H    "       "          CH.sub.3   Na                                         H    CH.sub.3                                                                              "          C.sub.2 H.sub.4 OH                                                                       Na                                         CH.sub.3                                                                           CH.sub.3                                                                              "          C.sub.2 H.sub.4 OCOCH.sub.3                                                              Na                                         CH.sub.3                                                                           "       5-CH.sub.3 CH.sub.3   K                                          CH.sub.3                                                                           C.sub.6 H.sub.5                                                                       5-Cl       H          "                                          C.sub.4 H.sub.9n                                                                   C.sub.6 H.sub.5                                                                       5-NHCOCH.sub.3                                                                           C.sub.2 H.sub.4 CN                                                                       H                                          C.sub.4 H.sub.9n                                                                   "       5-OCH.sub.3                                                                              CH.sub.3   "                                          C.sub.4 H.sub.9n                                                                   "       H          C.sub.2 H.sub.4 CONH.sub.2                                                               Na                                         C.sub.4 H.sub.9n                                                                   "       H          C.sub.2 H.sub.4 NHCOCH.sub.3                                                             Na                                         C.sub.4 H.sub.9n                                                                   "       H          C.sub.3 H.sub.6 NHCONHC.sub.2 H.sub.5                                                    Na                                         C.sub.4 H.sub.9n                                                                   C.sub.6 H.sub.5                                                                       H          C.sub.2 H.sub.5                                                                          Na                                         C.sub.4 H.sub.9n                                                                   C.sub.6 H.sub.5                                                                       H          CH.sub.3   Na                                         C.sub.4 H.sub.9n                                                                   CH.sub.3                                                                              6-CH.sub.3 CH.sub.3   "                                          C.sub.4 H.sub.9n                                                                   CF.sub.3                                                                              "          C.sub.6 H.sub.5                                                                          "                                          C.sub.2 H.sub.5                                                                    C.sub.6 H.sub.5                                                                       H          C.sub.2 H.sub.5                                                                          H                                          C.sub.2 H.sub.5                                                                    C.sub.6 H.sub.5                                                                       H          H          Na                                         C.sub.2 H.sub.5                                                                    CONH.sub.2                                                                            "          CH.sub.3   "                                          C.sub.2 H.sub.5                                                                    CH.sub.3                                                                              "          CH.sub.3   "                                          C.sub.2 H.sub.5                                                                    Cl      5-OC.sub.2 H.sub.5                                                                       "          "                                          C.sub.2 H.sub.5                                                                    CH.sub.3                                                                              "          H          "                                          C.sub.2 H.sub.5                                                                    C.sub.6 H.sub.4p-Br                                                                   H          H          "                                          C.sub.2 H.sub.5                                                                    C.sub.6 H.sub.5                                                                       "          C.sub.2 H.sub.4 CONH.sub.2                                                               K                                          C.sub.2 H.sub.5                                                                    C.sub.6 H.sub.4p-OCH.sub.3                                                            "          C.sub.2 H.sub.4 CN                                                                       K                                          C.sub.2 H.sub.5                                                                    "       6-C.sub.6 H.sub.11                                                                       C.sub.2 H.sub.4 SO.sub.2 NH.sub.2                                                        "                                          C.sub.3 H.sub.7n                                                                   C.sub.2 H.sub.4 CN                                                                    4-OC.sub.6 H.sub.5                                                                       C.sub.2 H.sub.4 N(COCH.sub.3).sub.2                                                      "                                          C.sub.3 H.sub.7n                                                                   C.sub.2 H.sub.4 OCOCH.sub.3                                                           5-SCH.sub.3                                                                              C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2 H.sub.5                                               K                                          C.sub.3 H.sub.7n                                                                   CH.sub.3                                                                              5-SC.sub.6 H.sub.5                                                                       C.sub.2 H.sub.4 SO.sub.2 NHC.sub.2 H.sub.5                                               K                                          CH.sub.3                                                                           "       5-NHCOOCH.sub.3                                                                          C.sub.2 H.sub.4 OH                                                                       Na                                         CH.sub.3                                                                           C.sub.3 H.sub.7                                                                       6-NHSO.sub.2 CH.sub.3                                                                    C.sub.2 H.sub.4 CN                                                                       Na                                         CH.sub.3                                                                           CH.sub.3                                                                              6-OCH.sub.3, 5-NHCOCH.sub.3                                                              C.sub.2 H.sub.4 OCOCH.sub.3                                                              NH.sub.4                                   CH.sub.3                                                                           C.sub.2 H.sub.5                                                                       6-NHCOCH.sub.2 Cl                                                                        C.sub.6 H.sub.11                                                                         K                                          CH.sub.3                                                                           OH      6-NHCOC.sub.2 H.sub.4 OH                                                                 C.sub.2 H.sub.4 OH                                                                       K                                          H    SO.sub.2 NH.sub.2                                                                     "          CH.sub.2 C.sub.6 H.sub.5                                                                 K                                          H    SO.sub.2 NHC.sub.2 H.sub.5                                                            6-NHCONHC.sub.2 H.sub.5                                                                  C.sub.2 H.sub.4 CN                                                                       NH.sub.4                                   H    OC.sub.6 H.sub.11                                                                     6-NHCON(C.sub.2 H.sub.5).sub.2                                                           C.sub.2 H.sub.5                                                                          K                                          CH.sub.3                                                                           SC.sub.2 H.sub.5                                                                      6-CH.sub.3 C.sub.2 H.sub.4 NHCOCH.sub.3                                                             K                                          CH.sub.3                                                                           CONHC.sub.2 H.sub.5                                                                   6-NHCOCH.sub.3                                                                           C.sub.2 H.sub.4 CONH.sub.2                                                               "                                          CH.sub.3                                                                           OCH.sub.3                                                                             H          C.sub.2 H.sub.4 NHCOCH.sub.3                                                             Na                                         C.sub.4 H.sub.9n                                                                   NHOCC.sub.2 H.sub.5                                                                   "          "          "                                          C.sub.4 H.sub.9n                                                                   C.sub.6 H.sub.4p-CH.sub.3                                                             6-OH       "          H                                          __________________________________________________________________________

                  TABLE 5                                                         ______________________________________                                         ##STR11##                                                                        R.sup.1   R.sup.9      R.sup.10  M                                        ______________________________________                                        H         C.sub.6 H.sub.5                                                                            H           Na                                         CH.sub.3  "            CH.sub.3    Na                                         CH.sub.3  CH.sub.3     C.sub.6 H.sub.5                                                                           Na                                         C.sub.4 H.sub.9n                                                                        C.sub.6 H.sub.5                                                                            H           NH.sub.4                                   C.sub.4 H.sub.9n                                                                        C.sub.6 H.sub.5                                                                            H           Na                                         C.sub.4 H.sub.9n                                                                        "            CH.sub.3    "                                          C.sub.4 H.sub.9n                                                                        "            H           H                                          C.sub.2 H.sub.5                                                                         CH.sub.3     "           Na                                         C.sub.2 H.sub.5                                                                         CH.sub.3     C.sub.6 H.sub.5                                                                           Na                                         C.sub.2 H.sub.5                                                                         C.sub.6 H.sub.5                                                                            CH.sub.3    Na                                         C.sub.2 H.sub.5                                                                         C.sub.6 H.sub.5                                                                            "           NH.sub.4                                   C.sub.2 H.sub.5                                                                         CH.sub.3     H           K                                          C.sub.2 H.sub.5                                                                         C.sub.6 H.sub.4p-Br                                                                        "           K                                          C.sub.3 H.sub.7n                                                                        C.sub.6 H.sub.4p-OCH.sub.3                                                                 "           K                                          C.sub.3 H.sub.7n                                                                        "            Br          K                                          C.sub.3 H.sub.7n                                                                        C.sub.2 H.sub.4 CN                                                                         "           K                                          CH.sub.3  C.sub.2 H.sub.4 OCOCH.sub. 3                                                               "           K                                          CH.sub.3  CONH.sub.2   C.sub.2 H.sub.5                                                                           K                                          CH.sub.3  SCN          C.sub.2 H.sub.5                                                                           K                                          CH.sub.3  SO.sub.2 C.sub.2 H.sub.5                                                                   C.sub.6 H.sub.5                                                                           K                                          CH.sub.3  OCOCH.sub.3  C.sub.6 H.sub.4p-CH.sub.3                                                                 K                                          H         CONHC.sub.2 H.sub.5                                                                        "           K                                          H         OH           H           K                                          H         SO.sub.2 NH.sub.2                                                                          CONHC.sub.2 H.sub.5                                                                       K                                          CH.sub.3  SO.sub.2 NHC.sub.2 H.sub.5                                                                 CH.sub.3    K                                          CH.sub.3  OC.sub.6 H.sub.11                                                                          C.sub.2 H.sub.5                                                                           K                                          CH.sub.3  C.sub.2 H.sub.5                                                                            SCN         K                                          C.sub.4 H.sub.9n                                                                        CONHC.sub.2 H.sub.5                                                                        CONH.sub.2  K                                          C.sub.4 H.sub.9n                                                                        OCH.sub.3    CH(CH.sub.3).sub.2                                                                        K                                          C.sub.4 H.sub.9n                                                                        NHOCC.sub.2 H.sub.5                                                                        C.sub.6 H.sub.5                                                                           K                                          C.sub.4 H.sub.9n                                                                        "            C.sub.2 H.sub.5                                                                           H                                          ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                         ##STR12##                                                                      R.sup.1   R.sup.4         R.sup.11   M                                      ______________________________________                                        H       H               CH.sub.3     K                                        H       H               C(CH.sub.3).sub.3                                                                          "                                        H       H               CF.sub.3     "                                        CH.sub.3                                                                              H               COOC.sub.2 H.sub.5                                                                         H                                        CH.sub.3                                                                              H               CONHC.sub.2 H.sub.5                                                                        Na                                       CH.sub.3                                                                              H               C.sub.6 H.sub.5                                                                            K                                        C.sub.4 H.sub.9n                                                                      C.sub.6 H.sub.5 CH.sub.3     "                                        C.sub.4 H.sub.9n                                                                      "               C(CH.sub.3).sub.3                                                                          NH.sub.4                                 C.sub.4 H.sub.9n                                                                      "               C.sub.6 H.sub.5                                                                            Na                                       C.sub.4 H.sub.9n                                                                      "               C.sub.6 H.sub.9p-OCH.sub.3                                                                 "                                        C.sub.4 H.sub.9n                                                                      C.sub.6 H.sub.4p-SO.sub.2                                                                     CH.sub.3     "                                        C.sub.4 H.sub.9n                                                                      CH.sub.3 SO.sub.2                                                                             "            "                                        C.sub.4 H.sub.9n                                                                      C.sub.2 H.sub.5 SO.sub.2                                                                      "            "                                        C.sub.4 H.sub.9n                                                                      H               CH.sub.3     K                                        C.sub.4 H.sub.9n                                                                      H               C.sub.6 H.sub.4p-OCH.sub.3                                                                 "                                        C.sub.2 H.sub.5                                                                       H               CF.sub.3     "                                        C.sub.2 H.sub.5                                                                       H               COOC.sub.2 H.sub.5                                                                         NH.sub.4                                 C.sub.2 H.sub.5                                                                       H               C.sub.2 H.sub.5                                                                            Na                                       C.sub.2 H.sub.5                                                                       H               C.sub.6 H.sub.5                                                                            K                                        C.sub.2 H.sub.5                                                                       C.sub.6 H.sub.5 C.sub.6 H.sub.4p-Br                                                                        "                                        C.sub.2 H.sub.5                                                                       "               C(CH.sub.3).sub.3                                                                          H                                        C.sub.2 H.sub.5                                                                       "               C.sub.6 H.sub.11                                                                           Na                                       C.sub.2 H.sub.5                                                                       "               C.sub.6 H.sub.5                                                                            Na                                       C.sub.2 H.sub.5                                                                       C.sub.6 H.sub.5 SO.sub.2                                                                      CH.sub.3     Na                                       C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5 SO.sub.2                                                                      "            K                                        C.sub.3 H.sub.7n                                                                      CH.sub.3 CO     "            K                                        C.sub.3 H.sub.7n                                                                      C.sub.6 H.sub.5 CO                                                                            CH.sub.3     K                                        C.sub.3 H.sub.7n                                                                      CH.sub.3        CONH.sub.2   K                                        CH.sub.3                                                                              C.sub. 2 H.sub.4 OH                                                                           C.sub.2 H.sub.5                                                                            K                                        CH.sub.3                                                                              C.sub.2 H.sub.4 CN                                                                            "            K                                        CH.sub.3                                                                              C.sub.2 H.sub.4 OCOCH.sub.3                                                                   "            K                                        CH.sub.3                                                                              C.sub.6 H.sub.11                                                                              CF.sub.3     K                                        CH.sub.3                                                                              C.sub.2 H.sub.4 OH                                                                            C.sub.6 H.sub.4p-Cl                                                                        K                                        H       CH.sub.2 C.sub.6 H.sub.5                                                                      CONHC.sub.2 H.sub.5                                                                        K                                        H       C.sub.2 H.sub.4 CN                                                                            CH(CH.sub.3).sub.2                                                                         K                                        H       C.sub.2 H.sub.5 "            K                                        CH.sub.3                                                                              C.sub.2 H.sub.4 NHCO.sub.2 C.sub.2 H.sub.5                                                    C.sub.2 H.sub.5                                                                            K                                        CH.sub.3                                                                              C.sub.2 H.sub.4 CONH.sub.2                                                                    CH.sub.3     K                                        CH.sub.3                                                                              C.sub.2 H.sub.4 NHCOCH.sub.3                                                                  C.sub.2 H.sub.5                                                                            K                                        C.sub.4 H.sub.9n                                                                      "               C.sub.6 H.sub.5                                                                            NH.sub.4                                 ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                         ##STR13##                                                                      R.sup.1  Q      Q'   R.sup.12    R.sup.13 M                                 ______________________________________                                        H      CO     CO     C.sub.6 H.sub.5                                                                           C.sub.6 H.sub.5                                                                        Na                                  H      CO     CO     NH.sub.2    CH.sub.3 "                                   H      CN     CO     --          NHCO.sub.2 C.sub.2 H.sub.5                                                             K                                   CH.sub.3                                                                             CN     CO     --          CH.sub.2 OH                                                                            Na                                  CH.sub.3                                                                             CN     CO     --          CH.sub.3 Na                                  CH.sub.3                                                                             CO     SO.sub.2                                                                             NH.sub.2    OC.sub.6 H.sub.5                                                                       Na                                  C.sub.4 H.sub.9n                                                                     CO     SO.sub.2                                                                             CH.sub.2 Cl OCH.sub.3                                                                              Na                                  C.sub.4 H.sub.9n                                                                     CN     SO.sub.2                                                                             --          C.sub.6 H.sub.5                                                                        Na                                  C.sub.4 H.sub.9n                                                                     CO     CO     CH.sub.2 C(CH.sub.3).sub.2 CH.sub.2                                                              "                                     C.sub.4 H.sub.9n                                                                     CO     CO     1,2-C.sub.6 H.sub. 4 K                                   C.sub.4 H.sub.9n                                                                     CO     CO     C.sub.2 H.sub.5                                                                           OC.sub.2 H.sub.5                                                                       K                                   C.sub.4 H.sub.9n                                                                     CO     CO     CH.sub.3    NH.sub.2 K                                   C.sub.4 H.sub.9n                                                                     CO     CO     NHC.sub.2 H.sub.5                                                                         NH.sub.2 K                                   C.sub.4 H.sub.9n                                                                     CO     CO     NHC.sub.2 H.sub.5                                                                         CH.sub.3 K                                   C.sub.4 H.sub.9n                                                                     CO     SO.sub.2                                                                             NH.sub.2    C.sub.2 H.sub.5                                                                        NH.sub.4                            C.sub.2 H.sub.5                                                                      CO     CO     SC.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                        K                                   C.sub.2 H.sub.5                                                                      CO     CO     SCH.sub.2C.sub.6 H.sub.5                                                                  C.sub.2 H.sub.5                                                                        K                                   C.sub.2 H.sub.5                                                                      CO     CO     SC.sub.6 H.sub.11                                                                         OCH.sub.3                                                                              K                                   C.sub.2 H.sub.5                                                                      CO     CO     C.sub.6 H.sub.5                                                                           OCH.sub.3                                                                              K                                   C.sub.2 H.sub.5                                                                      CO     CO     NHCOC.sub.2 H.sub.5                                                                       NHCO.sub.2 C.sub.2 H.sub.5                                                             K                                   C.sub.2 H.sub.5                                                                      CO     CO     NHSO.sub.2 C.sub.2 H.sub.5                                                                NHCO.sub.2 C.sub.2 H.sub.5                                                             K                                   C.sub.2 H.sub.5                                                                      CO     CO     NHCOC.sub.6 H.sub.5                                                                       NHCO.sub.2 C.sub.2 H.sub.5                                                             K                                   C.sub.2 H.sub.5                                                                      CO     CO     OC.sub.2 H.sub.5                                                                          NHCO.sub.2 C.sub. 2 H.sub.5                                                            NH.sub.4                            ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                         ##STR14##                                                                                 OH                                                               R.sup.1                                                                           Position R.sup.2     M                                                    ______________________________________                                        H        2           5-Cl          Na                                         H        2           5-Cl          Na                                         H        2           5-OCH.sub.3   Na                                         CH.sub.3 3,4         H             K                                          CH.sub.3 2           5-OCH.sub.3   Na                                         CH.sub.3 2           "             "                                          C.sub.4 H.sub.9n                                                                       2           5-CH.sub.3    "                                          C.sub.4 H.sub.9n                                                                       3,4         H             "                                          C.sub.4 H.sub.9n                                                                       2           5-OCH.sub.3   K                                          C.sub.4 H.sub.9n                                                                       2           "             NH.sub.4                                   C.sub.4 H.sub.9n                                                                       2           5-NHC.sub.6 H.sub.5                                                                         Na                                         C.sub.4 H.sub.9n                                                                       2           5-NHCOCH.sub.3                                                                              Na                                         C.sub.2 H.sub.5                                                                        2           5-NHCOCH.sub.3                                                                              "                                          C.sub.2 H.sub.5                                                                        2           5-CH.sub.3    Na                                         C.sub.2 H.sub.5                                                                        2           5-OCH.sub.3   K                                          C.sub. 2 H.sub.5                                                                       2           5-Cl          Na                                         C.sub.2 H.sub.5                                                                        4           2-OCH.sub.3   K                                          C.sub.2 H.sub.5                                                                        3,4         H             Na                                         C.sub.3 H.sub.7n                                                                       3,4         H             Na                                         C.sub.3 H.sub.7n                                                                       2           3-NHCOCH.sub.3                                                                              Na                                         C.sub.3 H.sub.7n                                                                       2           "             K                                          CH.sub.3 2           5-CONHC.sub.2 H.sub.5                                                                       K                                          CH.sub.3 2           5-C.sub.6 H.sub.11                                                                          "                                          CH.sub.3 2           5-OC.sub.6 H.sub.5                                                                          NH.sub.4                                   CH.sub.3 2           5-SCH.sub.3   K                                          CH.sub.3 2           5-SC.sub.6 H.sub.5                                                                          K                                          H        2           5-NHCOOCH.sub.3                                                                             Na                                         H        2           5-NHSO.sub.2 CH.sub.3                                                                       Na                                         H        2           5-NHCOCH.sub.3                                                                              NH.sub.4                                   CH.sub.3 2           5-NHCOCH.sub.2 Cl                                                                           K                                          CH.sub.3 2           5-NHCOC.sub.2 H.sub.4 OH                                                                    K                                          CH.sub.3 2           5-Cl          K                                          C.sub.4 H.sub.9n                                                                       2           5-NHCONHC.sub.2 H.sub.5                                                                     NH.sub.4                                   C.sub.4 H.sub.9n                                                                       2           5-NHCON(C.sub.2 H.sub.5).sub.2                                                              K                                          C.sub.4 H.sub.9n                                                                       2           5-CH.sub.3    "                                          C.sub.4 H.sub.9n                                                                       2           5-NHCOCH.sub.3                                                                              "                                          C.sub.4 H.sub.9n                                                                       4           H             Na                                         ______________________________________                                    

                  TABLE 9                                                         ______________________________________                                         ##STR15##                                                                               OH                                                                   Posi-                                                                       R.sup.1                                                                         tion     R.sup.2                                                                              R.sup.14   M                                                ______________________________________                                        H      2      3-CO.sub.2 CH.sub.3                                                                        H            K                                     H      4      H            H            "                                     H      4      H            H            "                                     CH.sub.3                                                                             4      H            H            Na                                    CH.sub.3                                                                             2      H            H            K                                     CH.sub.3                                                                             2      3-CONH.sub.3 H            K                                     C.sub.4 H.sub.9n                                                                     2      3-CO.sub.2 CH.sub.3                                                                        H            Na                                    C.sub.4 H.sub.9n                                                                     2      H            6-SO.sub.2 N(CH.sub.3).sub.2                                                               Na                                    C.sub.4 H.sub.9n                                                                     2      "            6-SO.sub.2 NHC.sub.3 H.sub.6 OCH.sub.3                                                     Na                                    C.sub.4 Hn                                                                           2      "            6-SO.sub. 2 N(C.sub.2 H.sub.5).sub.2                                                       "                                     C.sub.4 H.sub.9n                                                                     2      "            H            "                                     C.sub.4 H.sub.9n                                                                     4      "            "            "                                     C.sub.4 H.sub.9n                                                                     2      3-CONH.sub.2 H            K                                     C.sub.2 H.sub.5                                                                      2      3-CO.sub.2 CH.sub.3                                                                        "            Na                                    C.sub.2 H.sub.5                                                                      2      H            "            NH.sub.4                              C.sub.2 H.sub.5                                                                      2      3-CO.sub.2 CH.sub.2 Cl                                                                     "            K                                     C.sub.2 H.sub.5                                                                      2      3-CO.sub.2 C.sub.2 H.sub.4 OH                                                              "            K                                     C.sub.2 H.sub.5                                                                      4      H            H            K                                     C.sub.2 H.sub.5                                                                      2      3-CONHC.sub.2 H.sub.5                                                                      "            NH.sub.4                              C.sub.2 H.sub.5                                                                      2      3-CON(C.sub.2 H.sub.5).sub.2                                                               "            K                                     C.sub.2 H.sub.5                                                                      2      3-CO.sub.2 C.sub.2 H.sub.5                                                                 "            "                                     C.sub.2 H.sub.5                                                                      2      3-CO.sub.2 CH(CH.sub.3).sub.2                                                              "            "                                     C.sub.3 H.sub.7n                                                                     2      H            "            "                                     ______________________________________                                    

                                      TABLE 10                                    __________________________________________________________________________     ##STR16##                                                                    R.sup.1                                                                            R.sup.16      R.sup.17                                                                             R.sup.2                                                                            R.sup.14                                                                           M                                         __________________________________________________________________________    H    C.sub.6 H.sub.11                                                                            H      H    H    K                                         H    C.sub.2 H.sub.4 CONH.sub.2                                                                  H      H    H    "                                         H    C.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2                                                         H      H    8-OH "                                         CH.sub.3                                                                           C.sub.2 H.sub.4 NHSO.sub.2 CH.sub.3                                                         H      H    H    Na                                        CH.sub.3                                                                           C.sub.2 H.sub.4 NH-CO-CH.sub.3                                                              H      3-OCH.sub.3                                                                        8-OH K                                         CH.sub.3                                                                           C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3                                                  H      H    H    K                                         C.sub.4 H.sub.9n                                                                   CH(CH.sub.3)C.sub.2 H.sub.5                                                                 H      H    H    Na                                        C.sub.4 H.sub.9n                                                                   CH(CH.sub.3)CH.sub.2 CH(CH.sub.3)CH.sub.3                                                   H      H    H    Na                                        C.sub.4 H.sub.9n                                                                   C.sub.6 H.sub.5                                                                             C.sub.2 H.sub.4 OH                                                                   2-OCH.sub.3                                                                        H    Na                                        C.sub.4 H.sub.9n                                                                   C.sub.2 H.sub.5                                                                             H      "    H    "                                         C.sub.4 H.sub.9n                                                                   CH.sub.2 CH(OH)CH.sub.2 OH                                                                  H      "    H    "                                         C.sub.4 H.sub.9n                                                                   C.sub.2 H.sub.4 SO.sub.2 NH.sub.2                                                           H      "    "    "                                         C.sub.4 H.sub.9n                                                                   (CH.sub.2).sub.6 NHCOCH.sub.3                                                               H      "    "    "                                         C.sub.4 H.sub.9n                                                                   C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH                                                         H      H    H    K                                         C.sub.2 H.sub.5                                                                    CH.sub.3      H      H    "    Na                                        C.sub.2 H.sub.5                                                                    C.sub.6 H.sub.11                                                                            H      "    "    Na                                        C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.4 CONH.sub.2                                                                  H      H    H    NH.sub.4                                  C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.4 SO.sub.2 CHCH.sub.2                                                         H      H    8-OCH.sub.3                                                                        K                                           C.sub.2 H.sub.5                                                                   ##STR17##    H      3-OC.sub.2 H.sub.5                                                                 K                                                C.sub.2 H.sub.5                                                                  C.sub.2 H.sub.4 NH-CO-CH.sub.3                                                              H      H    H    K                                         C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OCH.sub.3                                                  CH.sub.3                                                                             H    "    NH.sub.4                                  C.sub.2 H.sub.5                                                                    CH(CH.sub.3)C.sub.2 H.sub.5                                                                 CH.sub.3                                                                             H    "    K                                         C.sub.2 H.sub.5                                                                    CH(CH.sub.3)CH.sub.2 CH(CH.sub.3)CH.sub.3                                                   CH.sub.3                                                                             3-C.sub.2 H.sub.5                                                                  "    "                                         C.sub.2 H.sub.5                                                                    C.sub.6 H.sub.5                                                                             C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                     H    "    "                                         C.sub.3 H.sub.7n                                                                   C.sub.2 H.sub.5                                                                             "      H    "    "                                         __________________________________________________________________________

The invention has been described in detail with particular reference tocertain preferred embodiments thereof, but it will be understood thatvariations and modifications can be effected within the spirit and scopeof the invention.

We claim:
 1. A dye of the formula: ##STR18## wherein R¹ is hydrogen oralkyl; M is H⁺, Na⁺, Li⁺, K⁺ or NH₄ ⁺ ; and C is a coupler selected from##STR19## wherein R² and R¹⁴ each independently represents hydrogen or1-3 substituents selected from fluorine, chlorine, bromine, alkyl,cycloalkyl, alkoxy, phenoxy, alkylthio, arylthio, and radicals havingthe formula --NH--X--R³ in which X is --CO--, --COO--, or --SO₂ -- andR³ is selected from alkyl and alkyl substituted with halogen, hydroxy,phenoxy, aryl, cyano, cycloalkyl, alkylsulfonyl, alkylthio, alkanoyloxy,and alkoxy, and when X is --CO--, R³ also is selected from hydrogen,amino, alkylamino, alkylcarbamoyl, dialkylamino, arylamino, aryl, andfuryl;R⁴ and R⁵ are each selected from hydrogen, alkyl, aryl,cycloalkyl, and R⁴ and R⁵ combined as --CH₂ CH₂ CH₂ CH₂ CH₂ --, --CH₂CH₂ OCH₂ CH₂ --, --CH₂ CH₂ --S--CH₂ CH₂ --, or --CH₂ CH₂ --SO₂ --CH₂ CH₂--; R⁸ is one or two groups each selected from hydrogen, alkyl and alkylsubstituted with --CN, alkoxy, alkoxycarbonyl, alkoxycarbonyloxy,phenyl, cyclohexoxy, --OH, --Cl and Br; R⁹, R¹⁰ and R¹¹ are eachselected from hydrogen, alkyl, phenyl, phenyl substituted with 1-3substituents selected from Cl, Br, alkyl and alkoxy, alkylthio,benzylthio, cyclohexylthio, and phenylthio; Q and Q' are each selectedfrom --CO--, --SO₂, and --CN; R¹² and R¹³ are each selected fromhydrogen, alkyl, hydroxyalkyl, alkoxy, alkoxycarbonylamino,trifluoromethyl, phenyl, phenyl substituted with 1-3 substituentsselected from Cl, Br, alkyl and alkoxy, alkoxycarbonylalkyl, cyanoalkyl,amino, haloalkyl, alkylamino, alkylthio, benzylthio, cyclohexylthio,phenylthio, and R¹² and R¹³ combined as an alkylene bridge of 2 or 3carbons or as an arylene or cycloalkylene radical of 5-6 carbonsconnecting Q and Q'; R¹⁶ and R¹⁷ are selected from hydrogen, cycloalkyl,aryl, alkyl, alkyl substituted with alkoxy, hydroxy, alkoxyalkoxy,hydroxyalkoxy, carbamoyl, sulfamoyl, acylamido, or alkylsulfonyl, andaryl substituted with hydroxyalkyl; e is 1 or 2; t and t' are each 1 orzero and when t or t' is zero, the corresponding Q or Q' group is --CN;and wherein each of the aliphatic portions of the above alkyl,cycloaliphatic, alkoxy, alkanoyl, aryl and aryloxy groups areunsubstituted or substituted with 1-3 of the following: hydroxy;halogen; cyano; succinimido; glutarimido; phthalimido; 2-pyrrolidono;cyclohexyl; phenyl; phenyl substituted with alkyl, alkoxy, halogen,alkanoylamino, cyano or alkoxycarbonyl; alkanoylamino; vinylsulfonyl;acrylamido; phthalimidinyl; benzoylsulfonicimidyl; alkylsulfonamido;phenylsulfonamido; alkoxycarbonylamino; alkylcarbamoyloxy;alkoxycarbonyl; alkoxycarbonyloxy; ##STR20## wherein Y is --NH--,--NH--alkyl--, --O--, --S--, or --CH₂ O--; --S--R⁶ wherein R⁶ is alkyl,phenyl, phenyl substituted with halogen, alkyl, alkoxy, alkanoylamino,cyano, or alkoxycarbonyl, pyridyl, pyrimidinyl, benzoxazolyl,benzimidazolyl, benzothiazolyl, or ##STR21## --OXR³ ; --NH--X--R³ ;--X--R³ ; --CONR⁷ R⁷ ; --SO₂ NR⁷ R⁷ ; wherein R³ and X are as definedabove and each R⁷ is selected from H and R³ ; alkoxy; alkoxy substitutedwith hydroxy, cyano, alkanoyloxy, or alkoxy; phenoxy or phenoxysubstituted with one or more of alkyl, alkoxy or halogen.
 2. The dyeaccording to claim 1 having the formula ##STR22##
 3. The dye accordingto claim 1 having the formula ##STR23##
 4. The dye according to claim 1having the formula ##STR24##
 5. The dye according to claim 1 having theformula ##STR25##
 6. A dye according to claim 1 wherein C is a couplerof the formula ##STR26## wherein R², R⁴, and R⁵ are as defined therein.7. A dye according to claim 1 wherein C is a coupler of the formula##STR27## wherein R², R⁴, and R⁸ are as defined therein.
 8. A dyeaccording to claim 1 wherein C is a coupler of the formula ##STR28##wherein R², R⁴, and R⁸ are as defined therein.
 9. A dye according toclaim 1 wherein C is a coupler of the formula ##STR29## wherein R², R⁴,and R⁹ are as defined therein.
 10. A dye according to claim 1 wherein Cis a coupler of the formula ##STR30## wherein R⁹ and R¹⁰ are as definedtherein.
 11. A dye according to claim 1 wherein C is a coupler of theformula ##STR31## wherein R⁴ and R¹¹ are as defined therein.
 12. A dyeaccording to claim 1 wherein C is a coupler of the formula ##STR32##wherein Q, Q', t, t', R¹² and R¹³ are as defined therein.
 13. A dyeaccording to claim 1 wherein C is a coupler of the formula ##STR33##wherein e and R² are as defined therein.
 14. A dye according to claim 1wherein C is a coupler of the formula ##STR34## wherein R², R¹⁴, R¹⁶,and R¹⁷ are as defined therein.
 15. A dye according to claim 1 wherein Cis a coupler of the formula ##STR35## wherein e, R² and R¹⁴ are asdefined therein.